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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/007—Mixed salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/656—Manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/656—Manganese, technetium or rhenium
  • B01J23/6562—Manganese
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/896—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J25/00—Catalysts of the Raney type
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
  • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

• the present invention relates to obtaining higher alcohols by using a catalyst of the metal oxide type comprising gallium and a noble metal. Therefore, the present invention belongs to the field of catalytic processes for obtaining higher alcohols.
• US5300695 describes zeolites exchanged with cations of K, Na, Ba and Cs among others as catalysts in the condensation of low molecular weight alcohols, obtaining iso-butanol selectivities of 30-35% to a methanol conversion of 45 %.
• Several basic oxides containing Cu commonly used in the production of high molecular weight alcohols from synthesis gas (CO / H 2 ), have been tested in condensation reactions of methanol and ethanol to produce high molecular weight alcohols, however with a production of C 4 alcohols quite low.
• Another group of catalysts used are calcium phosphate based materials of the hydroxyapatite type (US20070255079).
• hydrotalcite-like materials as catalysts in alcohol condensation reactions, such as the Guerbet reaction, both in batch systems and in continuous fixed-bed reactors.
• Studies carried out with these mixed oxides of Mg and Al revealed that the catalytic activity of these materials depends on the nature, density and strength of the basic surface sites which, in turn, depend on the Mg / AI molar composition in the solid
• the international application WO2009026510 describes a process for the synthesis of n-butanol by a material derived from the thermal decomposition of a hydrotalcite preferably comprising magnesium and aluminum.
• the present invention relates to a process for obtaining higher alcohols in the presence of a catalyst that is a metal oxide comprising gallium.
• catalysts derived from hydrotalcite comprising gallium in its structure provide higher yields to n-butanol than its analogs without gallium,
• one aspect of the present invention relates to a method of obtaining (from now on the process of the invention) of higher C3-C15 alcohols, preferably between C 3 -C 8 , which comprises a contact step between at least a reagent selected from the list comprising methanol, ethanol (EtOH), propanol and isopropanol and a catalyst, wherein said catalyst is a metal oxide comprising the following metals:
• M1 is at least one bivalent metal selected from the list comprising Mg, Zn, Cu, Co, Mn, Fe, Ni and Ca,
• said catalyst contains a noble metal selected from the list comprising Pd, Pt, Ru, Rh and Re, preferably Pd.
• C3-C15 higher alcohols means any linear or branched alkyl chain with at least one hydroxy functional group and having between 3 and 15 carbon atoms.
• C3-C8 higher alcohols means any linear or branched alkyl chain with at least one hydroxy functional group and having between 3 and 8 carbon atoms.
• the higher alcohol will preferably be a C3, C 4 , C 5 , C6, C 7 or Cs.
• Non-limiting examples would be propanol, isopropanol, n-butanol, 2-butanol, 2-methyl-2-butanol, 3- methyl-1 -butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl- 1-Propanol, 3-methyl-
• 2-butanol 1,5-pentanediol, 2,4-pentanediol, 2,2-dimethyl-1, 3-propanediol, 1, 2- butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- butanediol, 1-heptane, 2-heptanol,
• bivalent metal or “trivalent metal” is meant a metal cation with a +2 or +3 charge, respectively.
• the catalyst is the metallic oxide which further comprises a metal M3, where M3 is at least one trivalent metal selected from the list comprising Al, La, Fe, Cr, Mn, Co and Ni.
• the metal oxide is obtained from the total or partial thermal decomposition of a hydrotalcite of the formula [M1 1- (x + y) M2 and M3 x (OH) 2 ] [A m " ( x + y ) / m .nH 2 0], where M1, M2 and M3 have been described above, A is at least one anion selected from the list comprising hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, p-toluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II), x is a value between 0 and 0.5, preferably x is a value between 0.1
• thermal decomposition means a chemical decomposition or structural change caused by the action of heat. This decomposition can be total or partial, depending on whether said decomposition is carried out in its entirety or if, on the contrary, it is partially carried out. This thermal decomposition can be carried out at temperatures above 150 ° C and in the presence of an oxidizing or non-oxidizing gas.
• the hydrotalcite is obtained by coprecipitation of at least one M1 compound and at least one composed of a trivalent metal selected from the list comprising M2 and M3, preferably the hydrotalcite is obtained by coprecipitation of compounds of M1, M2 and M3.
• This anion A can be introduced between the sheets of the resulting hydrotalcite.
• sodium and / or potassium salts thereof can be used.
• A is at least one anion selected from the list comprising carbonate, bicarbonate and hydroxide. The best results are obtained when coprecipitation is carried out at a pH greater than 7, preferably between 10 and 14.
• sodium and / or potassium hydroxide are preferably used to regulate the pH.
• soluble compound of M1, M2 and M3 is meant any salt which in contact with a solvent dissociates, preferably a polar solvent, more preferably water.
• soluble compounds of M1, M2 and M3 may be nitrates, halides, sulfates, carboxylates and in general oxoacids comprising M1, M2 or M3, preferably the soluble compounds of M1, M2 and M3 are nitrates.
• A is preferably at least one anion selected from the list comprising C0 3 2 “ , HC0 3 “ , 0 2 “ , OH “ , CI “ , NO 3 2” , CI “ , F, Br “ , I “ , CIO 4 “ , CH 3 COO “ , C 6 H 5 COO “ , and SO 4 2” , even more preferably CO3 2 “ , HCO 3 “ , O 2 " and OH “ .
• Another embodiment of the present invention is the process as described above where the thermal decomposition of the hydrotalcite is carried out by a calcination, preferably by an calcination in the atmosphere of oxygen, nitrogen or any of its mixtures.
• the calcination is carried out at a temperature between 250 ° C and 650 ° C, preferably between 350 ° C and 550 ° C.
• the thermal decomposition of the hydrotalcite is preferably carried out over a range of 0.5 to 48 hours, preferably 1 to 24 hours.
• This process can be carried out by heating hydrotalcite in a gaseous atmosphere and can be carried out in a static oven or in a calcination reactor with controlled gas flow, the latter being the preferred system.
• the gas can be an oxidizing gas or a non-oxidizing gas.
• oxidizing gases may include air and oxygen.
• non-oxidizing gases can be inert gases, such as nitrogen, argon, helium and reducing gases such as carbon dioxide, hydrogen and ammonia.
• the calcination is carried out in the presence of oxygen, nitrogen or mixtures thereof and even more preferably in the presence of oxygen and nitrogen.
• hydrotalcite type structure can be corroborated by X-ray diffraction analysis (XRD); while the composition (quantity and type of constituent) of the hydrotalcite or the corresponding mixed oxide obtained by thermal decomposition of said hydrotalcite can be determined by mass spectrometry with inductive coupling plasma source (ICP-MS) and chemical analysis, among others.
• ICP-MS inductive coupling plasma source
• the noble metal is added to the metal oxide by wet impregnation, impregnation at incipient volume or deposition-precipitation, even more preferably by impregnation at incipient volume.
• the incipient volume impregnation method or also called the incipient wetness impregnation method is based on the use of a minimum amount of liquid for impregnation, only that necessary to reach the maximum saturation of the solid correspondent.
• the best yields of n-butanol have been obtained when hydrotalcites with Ga are impregnated with Pd.
• Another embodiment of the present invention is the process as described above where the concentration of the noble metal in the metal oxide is 0.001% to 10% by weight with respect to the total metal oxide, preferably 0.01% to 5%.
• M2 in the event that M2 has not been incorporated into the hydrotalcite in the coprecipitation stage, M2 can be incorporated into the metal oxide at a post-synthesis stage by wet impregnation, impregnation at incipient volume. and / or deposition-precipitation. This incorporation can be carried out in a previous step or simultaneously to the addition of at least one noble metal selected from the list comprising Pd, Pt, Ru, Rh, preferably Pd and Pt, and even more preferably Pd.
• hydrotalcite-derived catalysts comprising gallium in their structure provide higher yields of n-butanol under a nitrogen atmosphere than their gallium-free analogs. Not only that, but they also show a higher TON than catalysts that have the same concentration of Pd without gallium in the structure. This data is an indication of the greater stability in reaction conditions of the catalysts of the invention.
• the catalysts of the invention exhibit butanol selectivities at a certain higher ethanol conversion than prior art catalysts.
• a calcination step is preferably a calcination in the atmosphere of oxygen, nitrogen or any of its mixtures.
• This calcination is preferably carried out at a temperature of 250 ° C to 650 ° C, and even more preferably from 350 ° C to 550 ° C.
• This calcination is preferably carried out over a range of 0.5 to 48 hours, preferably 1 to 24 hours, and even more preferably 1 to 6 hours.
• This process can be carried out by heating hydrotalcite in a gaseous atmosphere and can be carried out in a static oven or in a calcination reactor with controlled gas flow, the latter being the preferred system.
• the gas can be an oxidizing gas or a non-oxidizing gas.
• oxidizing gases may include air and oxygen.
• non-oxidizing gases can be inert gases, such as nitrogen, argon, helium and reducing gases such as carbon dioxide, hydrogen and ammonia.
• the calcination is carried out in the presence of oxygen, nitrogen or mixtures thereof and even more preferably in the presence of oxygen and nitrogen.
• the process of the invention further comprises a step of reduction after calcination of the hydrotalcite.
• the noble metal is reduced, which acts as one of the main active sites in the process.
• This reduction step is preferably carried out under an H 2 atmosphere and preferably at a temperature of 200 ° C to 500 ° C, more preferably 250 ° C to 450 ° C.
• This reduction is preferably carried out over a range of 0.5 to 48 hours, preferably 1 to 24 hours, and even more preferably 1 to 6 hours.
• the reduction takes place immediately before the step of contact with the reagent.
• Another embodiment of the present invention is the process as described. above where the higher alcohol is a C 4 , preferably n-butanol.
• higher C 3 -C 20 primary alcohols preferably C-C 2
• higher secondary alcohols C3-C 2 or, preferably C3-C11 can also be obtained.
• the superior alcohol that will be obtained will be at least a C 4 .
• the hydroxy function of said upper secondary alcohols will preferably be located in C 2 .
• C 2 -C 6 aldehydes can also be obtained.
• the major by-products are preferably ethanal, 2-butanol, butanal, 1-hexanol, 2-hexanol, hexanal, 1-octanol, 2-octanol and octanal.
• the reagent is ethanol, methanol or any of its mixtures, preferably ethanol.
• the contact between the reagent and the catalyst is carried out in a reactor selected from the list comprising discontinuous reactor, continuous stirred tank reactor, continuous fixed bed reactor and continuous boiling bed reactor , preferably in a batch reactor.
• the contact between the reagent and the catalyst is carried out at a temperature between 50 ° C and 450 ° C, preferably between 100 ° C and 300 ° C.
• the weight ratio of the reagent to the catalyst is preferably from 2 to 200, preferably from 5 to 100.
• it is carried out for a period of time between 2 minutes and 200 hours, preferably between 1 hour and 100 hours.
• the contact between the reagent and the catalyst is carried out at a pressure of up to 120 bars, preferably between 20 and 80 bars.
• the contact between the reagent and the catalyst is carried out under an atmosphere of nitrogen, argon, hydrogen or any of its mixtures, preferably under an atmosphere of nitrogen and hydrogen.
• nitrogen, argon, hydrogen or any of its mixtures preferably under an atmosphere of nitrogen and hydrogen.
• Another embodiment of the present invention is the process as described above, which further comprises a step of separating the unreacted reagents from the higher C3-C15 alcohols obtained.
• said unreacted reagents are recycled to the contact step between reagents and catalyst, and more preferably, the unreacted reagent comprises ethanol. Even more preferably, the unreacted reagent is ethanol. Recirculation of unreacted reagents decreases waste production.
• Another embodiment of the present invention is the process as described above, which further comprises a step of separating intermediates from the higher C3-C15 alcohols obtained.
• said intermediate products are recirculated to the contact stage between reagents and catalyst.
• intermediate product in the context of the invention refers to any compound that is formed from the reagents and which can then be converted into higher C3-C15 alcohols. If it does not later become higher C3-C15 alcohols, the intermediate product can also be called a byproduct.
• the term “intermediate product” refers to aldehyde intermediates.
• the intermediate aldehyde is methanal, if it is ethanol, it is acetaldehyde (also called ethanal) and if it is propanol, propanal. More preferably, the intermediate product comprises acetaldehyde. Even more preferably, the intermediate product is acetaldehyde.
• Acetaldehyde is formed as an intermediate in the dimerization of ethanol as shown:
• acetaldehyde can optionally be recirculated and / or fed from an external source.
• acetaldehyde is obtained from the dehydration of ethanol. More preferably, this ethanol dehydration process is carried out at the same time as the main procedure to obtain higher C3-C15 alcohols.
• Fig. 1 Comparative graph of the selectivities of the Pd / HT-4 and Pd / Ga-HT-4 catalysts under N 2 atmosphere as a function of conversion.
• Fig. 2 Comparative graph of the selectivities of the catalysts Pd / HT-4 and Pd / Ga-HT-4 in an atmosphere of N 2 and H2 depending on the conversion. Legend as in Fig. 1.
• Fig. 3 Procedure diagram for obtaining butanol from ethanol with unreacted ethanol recirculation and acetaldehyde, B: Pump; C: heat exchanger; EtOH: ethanol; EtOH + CH 3 CHO: recirculation of ethanol and acetaldehyde; C: compressor; ButOH: butanol; Pg: purge; A: water; SP: other by-products; 1: Catalytic condensation reactor; 2: gas / liquid separation; 3: Dehydration; 4: Ethanol column; 5: Butanol refining.
• the first solution contained 36.45g of Mg (NO 3 ) 2 .6H 2 O and 13.60g of AI (NO 3 ) 3 .9H 2 O, dissolved in 67.79 g of MilliQ water, having a molar concentration of Al + Mg of 1.5.
• the second solution contained 12.53g of NaOH and 16.16g of Na 2 C0 3 in 89.63g of MilliQ water, and was used to produce adequate precipitation of the Al and Mg species, and to set the pH of the mixture total at " 13. Both solutions were added at a total flow rate of 30 ml / h for approx. 4 h, to a vessel under vigorous stirring at room temperature.
• the gel formed was aged at room temperature for 1-2 hours, then filtered and washed with distilled water until the carbonate was not detected in the filtered liquid (at pH ⁇ 7). Subsequently, the solid was dried in an oven at 60 ° C for 14-16 h, obtaining a mixed oxide called HT-4 with a Mg / AI ⁇ 3.8 molar ratio and a surface area (BET method) of 257 m 2 / g.
• the BET method refers to the Brunauer-Emmett-Teller isotherm method.
• the first solution contained 29.89 g of Mg (NO 3 ) 2 .6H 2 O, 10.90 g of AI (NO 3 ) 3 .9H 2 O and 0.06 g of Ga (NO 3 ) 3 .9H 2 Or, dissolved in 55.18 g of MilliQ water, having a molar concentration of (AL + Mg + Ga) of 1.5.
• the second solution contained 12.52g of NaOH and 10.52g of Na 2 C0 3 in 72.60g of MilliQ water, and was used to produce adequate precipitation of the Mg, Al and Ga species, and to fix the pH of the total mixture at * 13.
• Both solutions were added at a total flow rate of 30 ml / h for approximately 4 hours to a vessel under vigorous stirring at room temperature.
• the gel formed was aged at room temperature for 1-2 hours, then filtered and washed with distilled water until the carbonate was not detected in the filtered liquid (at pH ⁇ 7). Subsequently, the solid was dried in an oven at 60 ° C for 14-16h.
• the hydrotalcite (Ga-HT-4) obtained was calcined in air at 450 ° C for 3-4 h, obtaining a mixed oxide with a Mg / AI ⁇ 3.8 molar ratio, with a Ga content of 0.29% by weight (measured by chemical analysis and by ICP-MS), and with a surface area (BET method) of 262 m 2 / g.
• the resulting Pd / Ga / HT-4 material characterized by chemical analysis and by ICP-MS, contained " 0.74% by weight of Pd and ⁇ 0.48% by weight of Ga.
• Example 12 Catalyst synthesis 0.74% Pd / 0.29% Ga / HT-4
• the incorporation of Pd (1.0% by weight, theoretical) to the solid obtained was carried out by the incipient impregnation method at pore volume, using in this case 0.095g of Pd (NH 3 ) 4CI 2 .6H 2 0 dissolved in 1,500g of MilliQ water to impregnate 1,540g of solid obtained in the first impregnation.
• the final solid was dried in an oven at 100 ° C for 14-16h, then calcined in air at 450 ° C for 3-4h, and then reduced to 350 ° C in an H 2 atmosphere for 3 h before its catalytic application.
• the resulting Pd / Ga / HT-4 material characterized by chemical analysis and by ICP-MS, contained " 0.74% by weight of Pd and " 0.29% by weight of Ga.
• This catalyst was synthesized to illustrate the hydrotalcite type Cu catalysts, such as those mentioned in the application WO2009026523.
• Various catalysts with different concentrations of Cu were synthesized, and the catalyst that provided the best results, selectivity and conversion, was chosen for comparison with the catalysts of the invention.
• the first solution contained 28.73 g of Mg (N0 3 ) 2 .6H 2 0, 10.50 g of AI (N0 3 ) 3 .9H 2 0 and 1.20 g of Cu (N0 3 ) 2 .3H 2 0, dissolved in 56.25 g of MilliQ water, having a molar concentration of (Al + Mg + Cu) of 1.5.
• the second solution contained 12.72 g of NaOH and 10.25 g of Na 2 CO 3 in 73.71 g of water MilliQ, and was used to produce adequate precipitation of the Mg, Al and Cu species, and to set the pH of the total mixture to " 13.
• This catalyst was synthesized to illustrate the hydrotalcite-type catalysts with Co, such as those mentioned in US20100160693.
• Various catalysts with different concentrations of Co were synthesized, and the catalyst that provided the best results, selectivity and conversion, was chosen for comparison with the catalysts of the invention.
• the first solution contained 28.82 g of Mg (NO 3 ) 2 » 6H2O, 14.05 g of ⁇ ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 20 and 1.17 g of Co (NO 3 ) 2 « 6H2O dissolved in 58.54 g of MilliQ water, having a molar concentration of (Al + Mg + Cu) of 1.5.
• the second solution contained 13.81 g of NaOH and 10.87 g of Na 2 C0 3 in 77.91 g of MilliQ water, and was used to produce adequate precipitation of the Mg, Al and Cu species, and to fix the pH of the total mixture at " 13.
• This catalyst was synthesized to illustrate the hydrotalcite type catalysts with Ni, such as those cited in US20100160693. Various catalysts with different concentrations of Ni were synthesized, and the catalyst that provided the best results, selectivity and conversion, was chosen for comparison with the catalysts of the invention.
• the first solution contained 29.71 g of Mg (N0 3 ) 2 * 6H 2 0, 10.81 g of ⁇ ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 and 0.78 g of ⁇ ( ⁇ 0 3 ) 2 ⁇ 6 ⁇ 2 0, dissolved in 56.54 g of MilliQ water, having a molar concentration of (Al + Mg + Cu) of 1.5.
• the second solution contained 12.85 g of NaOH and 10.37 g of Na 2 C0 3 in 74.33 g of MilliQ water, and was used to produce adequate precipitation of the Mg, Al and Ni species, and to fix the pH of the total mixture at " 13.
• Example 16 Comparison of catalytic activity of the catalysts of examples 1, 2, 5, 7 and 13-15 under N 2 atmosphere
• a 12-ml stainless steel autoclave reactor with Teflon-coated interior and with magnetic stirrer, 3500 mg of ethanol and 200 mg of one of the catalytic materials of examples 1, 2, 5, 7 and 13- were introduced fifteen.
• the reactor was hermetically sealed, the system containing a connection to a pressure gauge (pressure gauge), another connection for the loading of gases and a third outlet that allowed samples to be taken at different time intervals.
• Liquid samples ( « 50 ⁇ ) were taken at different time intervals until 17-24 hours of reaction.
• the samples were filtered and diluted in a standard solution of 2% by weight chlorobenzene in acetonitrile and analyzed by gas chromatography on a GC-3900. They are equipped with an FID detector and a 60 m TRB-624 capillary column, calculating from the composition of the mixture obtained the conversion of ethanol into molar percentage (Conv. EtOH):
• Table 1 Catalytic activity of various mixed metal oxides in the transformation of ethanol to n-butanol in a nitrogen atmosphere.
• a TON Turn Over Number in (mol / mol Pd or Pt).
• Example 17 Comparison of catalytic activity of the catalysts of Examples 2-5 and 7-12 under N 2 atmosphere
• the samples were filtered and diluted in a standard solution of 2% by weight chlorobenzene in acetonitrile and analyzed by gas chromatography on a GC-3900. They are equipped with an FID detector and a 60 m TRB-624 capillary column, calculating from the composition of the mixture obtained the conversion of ethanol into molar percentage (Conv. EtOH): (initial moles of reagent - final moles of reagent) / (initial moles of reagent * 100), and the selectivities to n-butanol obtained in mole percent (Select. n-ButOH): (moles of n-butanol / moles of products Total) * 100. The total yield to n-butanol (Yield n-ButOH) is calculated:
• the catalysts of the invention exhibit butanol selectivities at a certain higher ethanol conversion than the state of the art catalysts in N 2 atmosphere.
• the catalysts of the invention allow lower concentrations of Pd to be achieved while maintaining high yields of n-butanol, compared to the prior art catalysts.
• Example 18 Comparison of catalytic activity of the catalysts of Examples 2-5 and 7-12 in the atmosphere of N2 and H2.
• the catalysts of the invention allow lower concentrations of Pd to be achieved while maintaining high yields of n-butanol, compared to the prior art catalysts.
• Example 19 Effect of co-absorption of intermediate acetaldehyde on the contact stage between the reagents and the catalyst of the invention
• a constant flow of the reagents described in Table 4 and 50 ml / min of N 2 was fed into a fixed bed stainless steel reactor 33 cm long and 0.83 cm in diameter, with a catalyst mass charge of 3300 mg of the catalytic material described in Example 7.
• the reactor was then connected to the synthesis loop, which contained a connector to a pressure gauge (gauge), another connector for reagent inlet and a third for outlet.
• the operating pressure in the reactor was controlled by a valve located in the output stream. Once the operating temperature was reached, the input current was fed to the reactor synthesis loop.
• LHSV liquid hourly space velocity
• LHSV liquid hourly space velocity

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• 2012
  • 2012-06-29 EP EP12382261.1A patent/EP2679304A1/fr not_active Withdrawn
• 2013
  • 2013-07-01 US US14/411,752 patent/US9475741B2/en active Active
  • 2013-07-01 ES ES13756520.6T patent/ES2545132T3/es active Active
  • 2013-07-01 WO PCT/ES2013/070448 patent/WO2014001597A1/fr not_active Ceased
  • 2013-07-01 KR KR1020157002188A patent/KR102100714B1/ko active Active
  • 2013-07-01 CN CN201380034303.9A patent/CN104736239B/zh active Active
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• 2014
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